Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—Polyurethanes from polyesters

Definitions

• the present invention relates to a moisture-curable polyurethane resin composition, an adhesive, and a laminate.
• Breathable waterproof functional clothing which has both moisture permeability and waterproofness, is a structure in which a moisture permeable film is bonded to fabric with an adhesive, and urethane adhesives are generally used as the adhesive because of their good adhesion to both the moisture permeable film and the fabric. Furthermore, among the urethane adhesives, the amount of use of solvent-free moisture-curing polyurethane resin compositions is gradually increasing due to recent global regulations on solvent emissions and residual solvents (see, for example, Patent Document 1).
• the problem that the present invention aims to solve is to provide a moisture-curable polyurethane resin composition that uses biomass raw materials to increase the biomass content and has excellent texture and adhesive properties.
• the present invention provides a moisture-curable polyurethane hot melt resin composition, which is characterized by containing a urethane prepolymer (i) having an isocyanate group, which is a reaction product of polyol (A) including polyester polyol (a1) made from biomass-derived sebacic acid and biomass-derived diethylene glycol, and polyisocyanate (B) and has a biomass degree of 40% or more.
• a urethane prepolymer i
• an isocyanate group which is a reaction product of polyol (A) including polyester polyol (a1) made from biomass-derived sebacic acid and biomass-derived diethylene glycol, and polyisocyanate (B) and has a biomass degree of 40% or more.
• the present invention also provides an adhesive that contains the moisture-curable polyurethane resin composition. Furthermore, the present invention also provides a laminate that has at least a substrate and a cured product of the moisture-curable polyurethane resin composition.
• the moisture-curing polyurethane resin composition of the present invention is made using biomass raw materials, has a high biomass content, and is an environmentally friendly material.
• the moisture-curing polyurethane resin composition of the present invention combines excellent texture and adhesiveness.
• the moisture-curable polyurethane hot melt resin composition used in the present invention is a reaction product of polyol (A) containing a specific polyester polyol and polyisocyanate (B), and contains urethane prepolymer (i) having an isocyanate group and a biomass ratio of 40% or more.
• the polyol (A) must contain polyester polyol (a1) made from biomass-derived sebacic acid and biomass-derived diethylene glycol. By using the specific polyester polyol (a1), the resin film becomes soft, and an excellent texture can be obtained even when the biomass content is increased.
• the biomass-derived sebacic acid may be, for example, that obtained by a known cleavage reaction of vegetable oils such as castor oil with caustic alkali.
• the sebacic acid may be, for example, commercially available as "Bio Seb” manufactured by Toyokuni Oil Co., Ltd.
• the biomass-derived diethylene glycol may be, for example, one obtained by a known method using waste molasses such as sugar cane as a raw material.
• waste molasses such as sugar cane as a raw material.
• diethylene glycol for example, "Bio DEG” manufactured by India Glycols is available as a commercially available product.
• polyester polyol (a1) may be used in combination as raw materials for the polyester polyol (a1).
• polybasic acids examples include succinic acid, adipic acid, azelaic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and anhydrides of these acids.
• These polybasic acids may be derived from biomass or from petrochemicals, and may be used alone or in combination of two or more.
• the amount of sebacic acid derived from biomass in the total polybasic acids is preferably 20 mol % or more, and more preferably 40 mol % or more.
• glycol compounds examples include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-
• These compounds may be derived from biomass or petrochemicals, and may be used alone or in combination of two or more.
• the amount of the biomass-derived diethylene glycol used in the total glycol compounds is preferably 20 mol% or more, and more preferably 40 mol% or more.
• the number average molecular weight of the polyester polyol (a1) is preferably 500 to 100,000, more preferably 700 to 50,000, and even more preferably 800 to 10,000, in order to obtain even better mechanical strength, texture, and adhesiveness.
• the number average molecular weight of the polyester polyol (a1) is a value measured by gel permeation chromatography (GPC).
• the polyol (A) contains the polyester polyol (a1) as an essential component, but may contain other polyols as necessary.
• the content of the polyester polyol (a1) in the polyol (A) is preferably 20% by mass or more, and more preferably 30 to 80% by mass.
• polyester polyols other than the polyester polyol (a1) for example, polyester polyols other than the polyester polyol (a1), polycarbonate polyols, polyether polyols, polybutadiene polyols, polyacrylic polyols, etc. can be used. These polyols may be used alone or in combination of two or more.
• one or more selected from the group consisting of polyester polyols made from phthalic acid, polyester polyols made from sebacic acid, and polyester polyols made from adipic acid, other than the polyester polyol (a1) are preferred, in terms of obtaining even better mechanical strength and adhesiveness.
• the number average molecular weight of the other polyols is, for example, 500 to 100,000.
• the number average molecular weight of the other polyols is a value measured by gel permeation chromatography (GPC).
• aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used.
• polyisocyanates can be used alone or in combination of two or more.
• aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, in that they provide even better reactivity, mechanical strength, and adhesiveness.
• the amount of polyisocyanate (B) used is preferably in the range of 5 to 40 mass % of the total mass of the raw materials constituting the urethane prepolymer (i), and more preferably in the range of 10 to 30 mass %.
• the hot melt urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and has an isocyanate group that can form a crosslinked structure by reacting with moisture present in the air or in the substrate to which the moisture-curable polyurethane hot melt resin composition is applied.
• the biomass degree of the hot melt urethane prepolymer (i) is 40% or more. As described above, in the present invention, by using a specific polyester polyol (a1), excellent texture and adhesiveness can be obtained even with a high biomass degree.
• the biomass degree of the hot melt urethane prepolymer (i) is more preferably 40 to 70%.
• the biomass degree of the hot melt urethane prepolymer (i) indicates the total weight ratio of the biomass-derived raw materials used in producing the hot melt urethane prepolymer (i) to the total weight of the hot melt urethane prepolymer (i).
• the hot melt urethane prepolymer (i) can be produced, for example, by adding the polyisocyanate (B) to a reaction vessel containing the polyol (A) and reacting them under conditions in which the isocyanate groups of the polyisocyanate (B) are in excess of the hydroxyl groups of the polyol (A).
• the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (B) to the hydroxyl group in the polyol (A) is preferably in the range of 1.2 to 5, and more preferably in the range of 1.5 to 3, in order to obtain even better mechanical strength, texture, and adhesiveness.
• the isocyanate group content (hereinafter abbreviated as "NCO%) of the hot melt urethane prepolymer (i) obtained by the above method is preferably in the range of 1.4 to 6, and more preferably in the range of 1.8 to 4.0, in order to obtain even better mechanical strength, texture, and adhesiveness.
• the NCO% of the hot melt urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.
• the moisture-curable polyurethane hot melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, but other additives may also be used as necessary.
• additives examples include light resistance stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, etc. These additives may be used alone or in combination of two or more.
• the moisture-curing polyurethane resin composition of the present invention is made using biomass raw materials, has a high biomass content, and is an environmentally friendly material. Furthermore, the moisture-curing polyurethane resin composition of the present invention combines excellent texture and adhesiveness.
• the laminate of the present invention has at least a fabric and a cured product of the moisture-curable polyurethane hot melt resin composition.
• the fabric may be, for example, a fiber substrate such as a nonwoven fabric, woven fabric, or knitted fabric made of polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, or a blend of these fibers; a nonwoven fabric impregnated with a resin such as a polyurethane resin; a nonwoven fabric further provided with a porous layer; or a resin substrate.
• a fiber substrate such as a nonwoven fabric, woven fabric, or knitted fabric made of polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, or a blend of these fibers
• a nonwoven fabric impregnated with a resin such as a polyurethane resin
• a nonwoven fabric further provided with a porous layer or a resin substrate.
• Methods for applying the moisture-curable polyurethane hot melt resin composition include, for example, methods using a roll coater, knife coater, spray coater, gravure roll coater, comma coater, T-die coater, applicator, dispenser, etc.
• the moisture-curable polyurethane hot melt resin composition After the moisture-curable polyurethane hot melt resin composition is applied, it can be dried and cured by known methods.
• the thickness of the cured product of the moisture-curable urethane hot melt resin composition is, for example, in the range of 5 to 500 ⁇ m.
• the moisture-curing polyurethane hot melt resin composition of the present invention is used as an adhesive for moisture-permeable, waterproof functional clothing.
• the thickness of the cured product of the moisture-curing polyurethane hot melt resin composition is, for example, in the range of 5 to 300 ⁇ m.
• Example 1 Into a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 112 parts by mass of polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Mills) and biomass-derived diethylene glycol (“Bio DEG” manufactured by India Glycols), number average molecular weight: 2,000, hereinafter abbreviated as "Bio PEs (1)”).
• Polyester polyol a reaction product of biomass-derived sebacic acid (“Bio Seb” manufactured by Toyokuni Oil Mills) and biomass-derived diethylene glycol (“Bio DEG” manufactured by India Glycols), number average molecular weight: 2,000, hereinafter abbreviated as "Bio PEs (1)”
• bioPEs (2) a reaction product of petroleum-derived 1,6-hexanediol and petroleum-derived orthophthalic acid, number average molecular weight; 3,500, hereinafter abbreviated as "bioPEs (3)”
• polyester polyol a reaction product of petroleum-derived 1,6-hexanediol and petroleum-derived orthophthalic acid, number average molecular weight; 2,000, hereinafter abbreviated as “other PEs (1)
• other PEs (1) a reaction product of petroleum-derived 1,6-hexanediol and petroleum-derived orthophthalic acid, number average molecular weight; 1,000, hereinafter abbreviated as “other PEs (2)
• other PEs (2) a reaction product of petroleum-derived neopentyl glycol and petroleum-derived orthophthalic acid, number average molecular weight; 1,000, hereinafter abbreviated as “other PEs (2)
• MDI diphenylmethane diisocyanate
• Example 2 In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 139 parts by mass of BioPEs (1) and 59 parts by mass of OtherPEs (2) were charged, and the mixture was dried under reduced pressure at 110°C to dehydrate until the moisture content was 0.05% by mass or less. Next, after cooling to 60°C, 56.7 parts by mass of MDI was added, the temperature was raised to 110°C, and the mixture was reacted for 2 hours until the isocyanate group content became constant, to obtain a urethane prepolymer (i-2), which was used as a moisture-curable polyurethane hot melt resin composition.
• i-2 urethane prepolymer
• Example 3 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 136 parts by mass of BioPEs (1), 136 parts by mass of BioPEs (2), and 68 parts by mass of other PEs (2), and dried under reduced pressure at 110 ° C. to dehydrate until the moisture content was 0.05% by mass or less.
• Example 4 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 61 parts by mass of bioPEs (1), 9 parts by mass of other PEs (1), and 17 parts by mass of other PEs (2), and dried under reduced pressure at 110 ° C. to dehydrate until the moisture content was 0.05% by mass or less.
• Example 5 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 64 parts by mass of BioPEs (1), 26 parts by mass of BioPEs (2), 13 parts by mass of other PEs (1), and 13 parts by mass of other PEs (2), and dried under reduced pressure at 110 ° C. to dehydrate until the moisture content was 0.05% by mass or less.
• Example 6 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 192 parts by mass of BioPEs (1), 32 parts by mass of BioPEs (2), 48 parts by mass of other PEs (1), and 48 parts by mass of other PEs (2), and dried under reduced pressure at 110 ° C. to dehydrate until the moisture content was 0.05% by mass or less.
• Example 7 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 49 parts by mass of BioPEs (1), 29 parts by mass of BioPEs (2), and 19 parts by mass of OtherPEs (1), and dried under reduced pressure at 110 ° C. to dehydrate until the moisture content was 0.05% by mass or less. Next, after cooling to 60 ° C., 20.3 parts by mass of MDI was added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours until the isocyanate group content became constant, to obtain a urethane prepolymer (i-7), which was used as a moisture-curable polyurethane hot melt resin composition.
• i-7 urethane prepolymer
• the number average molecular weights of the polyols used in the examples and comparative examples are values measured by gel permeation chromatography (GPC) under the following conditions.
• Measurement device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000” (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D.
• This processed fabric was cut to a width of 1 inch, and the peel strength was measured using a Tensilon (Tensilon universal testing machine "RTC-1210A” manufactured by Orientec Co., Ltd.) at a crosshead speed of 200 mm / min, and evaluated as follows. "Good”: 8N/cm or more "Poor”: Less than 8N/cm
• the moisture-curable polyurethane hot melt resin composition of the present invention was found to have a high biomass content, as well as excellent adhesion and texture.
• Comparative Example 1 which does not use polyester polyol (a1), had poor adhesion and texture.
• Comparative Example 2 used only a small amount of polyester polyol (a1) and had a biomass content below the range specified in the present invention, but the adhesion and texture were poor.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)
• Laminated Bodies (AREA)
• Adhesives Or Adhesive Processes (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91323187

Family Applications (1)

Country Status (4)

Citations (2)

• 2023
  • 2023-06-08 CN CN202380065541.XA patent/CN119790086A/zh active Pending
  • 2023-06-08 WO PCT/JP2023/021298 patent/WO2024116443A1/ja not_active Ceased
  • 2023-06-08 JP JP2024555171A patent/JP7677552B2/ja active Active
  • 2023-07-28 TW TW112128268A patent/TW202436420A/zh unknown

Patent Citations (2)

Also Published As

Similar Documents

Legal Events